Galactomannan gum based composition for sealing permeable formations

ABSTRACT

A COMPOSITION IS PROVIDED WHICH MAY BE EMPOLYED FOR THE SELECTIVE SEALING OF ERMEABLE FORMATIONS. THE COMPOSITION CONTAINS AT LEAST ONE PARTICUALTE GALACTOMANNAN GUM WHICH HAS BEEN TREATED TO RENDER THE GUM HYDROPHOBIC IN AQUEOUS SOLUTIONS HAVING A PH OF AT LEAST ABOUT 7.5; APH CONTROL AGENT, AND A WATER-SOLUBLE ORGANIC POLYMERIC SUSPENDING AGENT.

United States Patent 3,743,613 GALACTOMANNAN GUM BASED COMPOSETKON FOR SEALHNG PERMJEABLE FORMATKONS Albert W. Coulter, Jr., Daniel L. Gibson, and Kenneth H. Nirnerick, Tulsa, Okla, assignors to The Dow Chemical Company, Midland, Mich.

No Drawing. Continuation-impart of application Ser. No. 67,675, Aug. 3, 1970, which is a continuation-impart of application Ser. No. 623,232, Mar. 15, 1967. This application Feb. 5, 1971, Ser. No. 113,089

Int. Cl. (308d 9/06 US. Cl. 260-114 ST Claims ABSTRACT OF THE DISCLOSURE A composition is provided which may be employed for the selective sealing of permeable formations. The composition contains at least one particulate galactomannan gum which has been treated to render the gum hydrophobic in aqueous solutions having a pH of at least about 7.5; a pH control agent, and a water-soluble organic polymeric suspending agent.

CROSS-REFERENCE TO RELATED APPLICATIONS This application is a continuation-in-part of application Ser. No. 67,675, filed Aug. 3, 1970 which in turn is a continuation of application Ser. No. 623,232, filed Mar. 15, 1967 both applications now abandoned.

BACKGROUND OF THE INVENTION It is often desirous to temporarily seal or plug a permeable formation such as those located in a subterranean formation penetrated by an opening, e.g. borehole, so that other less permeable zones can be treated (i.e. fractured, acidized, etc.). Many methods and compositions have been employed for temporarily plugging or sealing these openings and passageways. Plugs and seals composed of various type materials are known and used. For example, fibrous, flaky or granular plugging agents, cement and viscous gels have been employed as plugging and sealing agents. These present methods and agents suffer from certain disadvantages. Fibrous materials, e.g. hay, sponges, etc., do not perform with predictable success and in many instances an impervious seal is not obtained in vuggs or fissures even when large quantities of material are pumped into the zone. Cementing requires an extended period of time both to allow the cement to set and then breaking through (drilling) the cement once circulation is again desired. Furthermore, cementing can be quite expensive and also can cause serious damage to producing formations. The more recent use of gels, such as cross-linked polysaccharides, has proved to be a great improvement over the former methods. However, difliculties found in the use of many of these gels include, instability of the gels with pH changes, nonuniformity of the gel solutions placed into the borehole, premature setting up (hydration and crosslinking) of the gels, a prolonged setting time, failure of the gel to break down within a certain predetermined period of time, high fluid loss of the unset gels, weakness of the set gel to extrusion caused by pressures and low resistance to elevated temperatures. There is therefore a need for a composition that can be emplaced as a readily pumpable slurry, thereafter sets up to form a mass capable of withstanding appreciable pressure, and subsequently liquefies so that the plug ceases to restrict the flow of fluids through the formation.

The present composition demonstrates uniformity, strength, predictable gellation setting times and breakdown times, good fluid retaining characteristics, and stability to a wide range of pH values. The composition may be prepared at the site of use employing locally available 3,743,0l3 Patented July 3, i973 Water supplies having a wide divergence in initial pH values, eg 3 to 10.

As employed herein a readily pumpable slurry is a slurry having rheological properties such that it can be pumped through feet of 2 inch inside diameter pipe at a minimum rate of about 2 bbls./minute with about 100 p.s.i. pumping pressure.

SUMMARY OF THE INVENTION The present invention comprises a granulated formulation; an aqueous slurry composition containing a portion of the constituents of the granulated formulation in solution, and a method of treating a permeable subterranean formation employing the slurry.

The granulated composition comprises a galactomannan gum which has been treated to render the gun hydrophobic (less hydrophillic than normal) than dispersed in an aqueous solution having a pH at least about 7.5; a pH control agent, and a water-soluble organic polymer suspending agent.

To employ the composition, it is mixed with a suilicient amount of water (as a carrier liquid) to make a readily pumpable slurry mixture. The slightly viscous slurry is injected (such as by pumping under pressure) into the formation to be sealed where it autogenously gels, i.e. sets up, to give a temporary, fluid-tight, pressure resistant, rigid gel which subsequently (after a period of time) disintegrates and ceases to plug.

PREFERRED EMBODIMENTS OF THE INVENTION In the practice of the present invention, the granulated composition comprises the following combination of constituents as parts by weight.

To make the novel slurry composition of the present invention, the granulated product (considered in pounds for illustrative purposes) is admixed with a sufiicient quantity of an aqueous solution to make an equivalent of 1000 gallons of slurry. An equivalent of about 50 pounds to about 2200 pounds of the composition defined by column one or from about 300 to about 1080 pounds of the preferred composition are admixed with a sufficient quantity of an aqueous solution to make about 1000 gallons of the indicated slurry.

Galactomannan gum as employed herein refers to those natural occurring polysaccharides derived from various endosperms of seeds. They are primarily composed of D-mannose and D-galactose units. They generally have similar physical properties, such as being soluble in water to form thick highly viscous solutions which usually can be gelled (cross-linked) by the addition of such inorganic salts as borax. Examples of galactomannan gums include tara, Hizachi, locust bean, paloverde, flame tree, guar, honey locust, green garrafin, Kentucky coffee bean, Japanese pagoda, prairie mimosa, indigo, Jenna, rattlebox, lucerne, clover, Fenergruk seeds and soy bean hulls. The gum is provided in a convenient particulate form generally smaller than that will be retained on a No. 20 mesh sieve (US. Standard Screen Series) but larger than that which passes through a No. 200 mesh sieve.

A hydrophobically treated galactomannan gum as employed herein is a galactomannan gum which has been treated in such a manner that the natural hydrophillic properties of the gum are inhibited sufliciently to allow the gum to be dispersed in an aqueous carrier liquid having a pH of about 7.5 or greater and the dispersion to be emplaced in a permeable zone before any substantial hydration (swelling or opening) of the gum occurs. The gum, however, swells in acidic solutions. The treating agent is herein referred to as a hydrophobing agent. To render the gumhydrophobic it may actually be pretreated to undergo some physical or chemical change prior to being placed in an aqueous carrier liquid (e.g., by being treated with a suitable hydrophobing agent) or it may be associated with (coated, admixed with, etc.) a hydrophobing agent which aifects the normal hydrophillic characteristic of the gum after being placed into the carrier liquid.

The hydrophobing agent may be any material capable of temporarily inhibiting the natural hydrophill-ic property of the gum. An example of a hydrophobing agent which affects the hydrophillic characteristic of the gum atfer being placed in the water is a material capable of liberating borate ions when added to water, e.g. alkali metal borates, sodium tetraborate (borax), sodium perborate, and sodium metaborate are preferred agents for use in the practice of the present invention. Details of one method for pretreating the gums with such a hydrophobing agent is taught in U.S. Pat. No. 2,868,664. Generally, a suificient amount of the boron containing agent is employed to bring the pH of an aqueous dispersion of the gum up to at least about 7.5. From about 0.5 to 1.0 percent by weight of such agent, based on the weight of the gum, is usually suflicient. Preferred gums are guar, tara or locust bean treated with borate ion liberating material.

Further information is available on the subject of borate-treated galactomannan gums in Chemical Abstracts vol. 43, part 3, column 6936c of September- November 1949 and in Industrial Gums by Whistler and BeMiller; published by the Academic Press, New York (1959'), page 339.

As indicated the hydrophobically treated galatomannan gum hydrates very slowly in aqueous solution having a neutral or alkaline pH but hydrates very quickly in acidic aqueous solutions.

The exact amount of gum employed for gel stability will depend to some extent on the temperature to which the set gel will be subjected in the formation to be sealed. At higher temperature levels, e.g. greater than about 125 F., a greater amount of the gum should be present. For example, above 125 F. a gel composition containing guar gum, polyacrylamide and sodium' dichromate at a total concentration of about 500 lbs/960 gallons of water has been found to be satisfactory whereas a concentration of only about 300 lbs/980 gallons of water was found practical for use at temperatures ranging from about 60 F. to 125 F.

The suspending agent comprises a water-soluble organic polymer which is readily dispersible in aqueous solutions having a neutral to alkaline pH, i.e. the initial pH of an aqueous dispersion of the slurry composition of the present invention, to form visually continuous solutions or dispersions.

The terminology water-soluble, organic polymer, as used herein refers to nonionic, anionic, cationic or ampholytic organic materials composed of a number of repeating units or mers. The useful polymers are characterized by dispersibility in water to form visually continuous solutions or dispersions. This include truly watersoluble polymers which disperse in water to provide homogeneous, transparent solutions subject to water dilution without phase separation. Also included within the meaning of water-soluble, as used herein, are the Water-swellable polymers which readily disperse in water to provide a highly disperse and visually continuous system of individually distinct, gel particles.

The water-soluble, organic polymers useful herein are av il ble in a w de ar y of ch mical c mposition. They may be obtained as natural polymeric products, by modification of natural polymers or by synthesis from polymerizable materials.

Water solubility is imparted to such polymers by the presence in and along the polymer chain of a number of hydrophilic moieties sufiicient to more than offset the otherwise hydrophobic character of the organic polymer. One class of such hydrophilic moieties includes the ionizable groups. Among these are the sulfate and sulfonate groups, carboxylate salt groups, amino and ammonium groups, the latter being inclusive of protonated as well as quaternary derivatives of the amines, e.g., mono-, diand trialkyl substituted ammonium salt groups, and phosphoric acid groups and monoand dibasic salts thereof. Whenever acid salts are referred to, those generally intended are the alkali metal, alkaline earth metal (water-soluble species thereof) and ammonium salts.

Another class of water-solubility imparting, hydrophilic moieties are such nonionizable groups as carboxamide and monoand dialkyl N-substituted carboxamides, having a total of up to about 8 carbons. Also of a hydrophilic nature, though less strongly than some of the aforementioned groups are hydroxyl, acetal, ketal, carbamate and lactamgroups. In any event, the polymers employed herein contain one or more of the aforedescribed hydrophilic moieties, and the like, in and along the polymer chain in a sufficient amount to render the resulting polymer water-soluble as defined above.

The polymers used in the invention are characterized by a high molecular weight. An adequate molecular weight is shown if the polymer can be obtained as a particulate solid and a 2 percent by weight solution of the polymer in water, at a pH of 7, has a viscosity measured with a Brookfield viscosimeter at 25 C. of at least 10 centipoises.

Technology for preparing the water-soluble polymers useful herein is known. Useful ethylenically polymerized polymers are described in Hedrick et al., U.S. Pat. 2,625,- 529, Aimone et al., U.S. Pat. 2,740,522 and Booth et al., U.S. Pat. 2,729,557. A variety of water-soluble polysaccharide derivatives are described in Gloor, U.S. Pat. 2,728,725. Water-soluble polyurethanes or chain extended polyols are taught in Honea et al., U.S. Pat. 3,054,778 and a variety of polycarbonates and polylactams in Hibbard et al., U.S. Pat. 3,044,982, Walles et al., U.S. Pat. 2,946,772, Vitales, U.S. Pat. 2,874,124 and Fong et al., U.S. Pat. 3,000,830. These are to mention but a few of the Well-known chemical avenues for the preparation of water-soluble, macromolecules. Further general descriptions of a variety of water-soluble, particulate macromolecules is contained in Davidson and Sittig, Water- Soluble Resins, Reinhold Publishing Corp., New York, 1962.

Preferred for use herein are water-soluble carbamoyl polymers. The most common forms of these are ethylenically polymerized polymers having attached along their polyalkane backbone a plurality of carbamoyl groups according to the formula:

wherein R and R are independently selected from the group of hydrogen and alkyl hydrocarbons with l to 4 carbons.

In particular, useful carbamoyl polymers includes the various water-soluble homopolymers and copolymers of acrylamide and methacrylamide. Qther carbamoyl polymers are the various water-soluble copolymers of N-substituted acrylamides such as N-methyl acrylamide, N-propyl acrylamide and N-butyl acrylamide. Still other carbamoyl polymers are prepared from the amides and half amides of maleic and fumaric acids. In general, any etl1- ylenically unsaturated and polymerizable monomer, which contains the carbamoyl group, may be employed in the preparation of the preferred carbamoyl polymers.

Best results are obtained, if at least about 25 mole percent of the polymerized mers have carbamoyl substituents. The balance of the comonomers used to prepare the copolymers can be provided in the form of any watersoluble, or water-insoluble, monoethylenically monomer copolymerizable therewith, so long as the total amount of Water-soluble monomers used is sufiicient to impart watersolubility to the finished polymer.

Other water-soluble polymers useful herein are the lightly cross-linked water-swellable polymers. Such crosslinking can be achieved by irradiation of linear, watersoluble polymers under conditions which promote crosslinking or by incorporating a small amount, e.g., up to 1% by weight, of a polyfunctional monomer into the polymerization recipe for a linear water-soluble polymer. Examples of such monomers, which may be copolymerized with monoethylenically unsaturated monomers, are methylenebisacrylamide; divinylbenzene, divinylether, divinylether of ethylene glycol and the like.

It is usually preferred that the suspending agent forms a near neutral or basic pH value when dispersed in an aqueous solution, i.e. one which will not cause an acidic pH and thus cause a premature swelling of the hydrophobically treated gum.

As indicated, one type of polymer found to be especially effective for this purpose is acrylamide polymers, including specifically polyacrylamide in varying degrees of hydrolysis and acrylamide copolymerized with one or more ethylenically unsaturated monomers such as acrylic acid, methacrylic acid, vinylsulfonic acid, vinylbenzylsulfonic acid, vinylbenzenesulfonic acid, and alkali and alkaline earth metal salts of such acids as described in US. Pat. 2,831,841, volumn 3, lines 34 to 45 and in U.S. Pat. 2,909,508, Examples 1 to 5.

Preferably the acrylamide polymer and acrylamide copolymers are those having a molecular weight such that when dispersed in a neutral or alkaline solution in an amount ranging from about 0.05 to about 1% by weight give a viscosity ranging from about 5 to about 200 centipoises at ambient temperatures. Preferably the viscosity is achieved within about minutes.

A particularly good suspending agent to employ is a polymer of from about 40 to 60 vinylpyrrolidone and 60 to 40 acrylamide (molar proportions) copolymerized by mixing between about 0.5 and 1.0 percent, by weight of the monomeric mixture of a cross-linking agent, e.g. methylenebisacrylamide, in the presence of between about 0.1 to 0.5 percent of a catalyst, e.g., azobisisobutyronitrile, in about a 10 to 40% aqueous dispersion.

Other water-soluble organic polymeric materials found effective are synthetic derivatives of cellulose and natural occurring water-soluble gums which are not affected by the presence of the hydrophobing agent and which produce a neutral to alkaline pH when dispersed in an aqueous solution, and modified starches having similar characteristics. Examples of natural gums which give a near neutral pH are the tree exudates including gum arabic, gum tragacanth, kutera gum, ghati, mesquite gum and the like. Cellulose derivatives which may be employed include, for example, methylcellulose, hydroxy propyl methylcellulose, cellulose ethers and esters, e.g., as set out in Encyclopedia of Chemical Technology, 2nd ed., vol. 4, page 618, John Wiley and Sons, New York, and other similar suspending agents. The exact agent employed is not critical to the practice of the invention except to the extent that it functions as defined hereinbefore.

Preferably the suspending agent is employed in an amount ranging from 0.05 to 10 percent by weight of the galactomannan employed. The exact amount of suspending agent will depend on the amount of hydrophobically treated gum employed, the temperature at which the slurry is to be employed, the other constiutents present in the slurry and the capacity of the injection equipment (e.g. pumps, blenders, etc.). The suspending agent allows for the formation of a slightly viscous slurry containing an event dispersion of the galactomannan gums therein and prevents fluid loss of the initial :slurries so that the gum can be emplaced into position in the permeable zone to be treated.

A pH control agent should be employed to maintain the pH of the initial slurry at least at about 7.5, preferably between about 8 and 12. This assures that the hydrophobically treated gum will not prematurely swell because of acidic conditions. A hydroxyl ion source and/or preferably a buffering agent may be employed.

The hydroxyl ion source may be any soluble 0r partially soluble hydroxide or carbonate that provides the desirable pH value in the slurry. Ca(OH) or Mg(OH) are preferred. Other acceptable materials are Bi(OH) Co(OH) Pb(OH) Ni(OH) lBa(OH) Sr(OH) and the alkali metal hydroxides and carbonates. The amount of the hydroxyl ion source to provide is that which is sufficient to yield a pH value in water of at least 7.5 and preferably between 8.0 and 12.

A buffering agent is preferably employed in the practice of the present invention to provide a buffered solution, i.e. a solution to which moderate amounts of either a strong base or acid may be added without causing any large change in pH value of the solution. A buffer solution usually contains a weak acid and a salt of the weak acid, an acid salt with a normal salt or a mixture of two acid salts. Examples of suitable buffering agents which may be employed to provide a buffered solution having the desired pH value are NaH PO Na HPO boric acid sodium hydroxide; acetic acid-sodium hydroxide; boric acid-borax; sodium carbonate-sodium bicarbonate; and sodium bicarbonate, or other like agents. By employing a buffering agent instead of merely a hydroxyl ion producing material a composition is provided which is more adapted to a wide variance of pH values found in local water supplies and the influence of acidic materials located in formations and the like. The pH control agent may be varied between about 0.6% and about 40% by weight of the treated gum employed.

The invention is not dependent: upon a theory as to its operation. It is not presently known how the various components of the fluid composition function during the gelatin stage. One theory is that the borate treated gum is crosslinked in aqueous solutions having a high pH thus minimizing its solubility and retarding its hydrolysis at a basic pH. At temperatures below 175 F. the strength of this crosslinking mechanism is sufiiciently strong to prevent hydrolysis. Above 175 'F., sufficient energy is present to allow hydrolysis and subsequent increases in viscosity of the aqueous system. It is known that galactomannans as a class are degraded by both acidic conditions and by heating to temperatures above F. Most rapid degradation occurs when both high temperatures and an acidic pH (less than 7.0) are present. It has been found that as a galactomannan water system is heated to an elevated temperature, i.e. above about 150 F., the pH of the solution decreases, becoming more acidic. It has been postulated that such. decrease in pH is the result of degradation of the galactomannan to produce various organic acids. It is, therefore, one purpose of this invention to recognize the foregoing hypothesis as applicable and to use various metal hydroxides as a means of neutralizing these organic acids as they are formed or by using a buffering agent to provide buffered solution. By neutralizing said Organic acids, or by providing a buffered solution the rate of degradation is retarded and the efiiciency of the gum system is extended. Frequently, fluid loss control agents are advantageously employed in the invention. The preferred material is silica flour (particles having an average size of less than about 1 micron and more desirably less than 0.1 micron). However, any substantially inert organic or inorganic pulverulent material (including starches and the like) may be employed as the fluid-loss control additive.

All the particulate constituents of the invention can be premixed and packaged in a convenient form. When ready for use, the particulate product is simply admixed with the necessary quantity of an aqueous solution to form an aqueous slurry of the treated gum. The slurry is then pumped into the formation to be sealed whereupon it sets up to form a firm plug. The set plug will break down after a predetermined period of time, thus allowing circulation through the treated area.

Since the ingredients are readily dispersible, the composition of the invention is easily prepared. It exhibits excellent low fluid-loss, thickens at a controllable rate which may be a relatively short time, if desirable, e.g. between A2 hour and 1 hour, or over a period of several hours if preferred, and thereafter liquefies within a few hours or longer, as desired.

In the following examples tests were conducted to show the desirable properties of the gelled composition of the invention. Thickening or gel time and plug life were determined for each series and are set out in the tables appearing hereinafter.

Thickening time, which herein is also considered the gel time, was determined according to Section 10, page 20 et seq., of API RP B (March 1965), employing the schedule designated herein for each series of tests. The gel time is also referred to herein sometimes as working time because it is the permissible time between admixture of the ingredients and the gelation during which the composition remains fluid.

The time between gelatin and breakdown or liquefaction of the gelled plug is called herein plug life. It was determined as follows:

A vertically held %-inch diameter 6-inch long steel pipe nipple, capped at the lower end, and containing a %-inch diameter steel ball, was nearly filled (allowing a little room for expansion) with a quantity of the slurry gelable composition. A cap was placed on the top of the nipple and it, with its contents put vertically in a bath, which had been preheated to a specified temperature. Thereafter, at -minute intervals, the nipple was inverted, the ball falling freely through the ungelled fluid. The inverting process was continued through the gelation stage,

The tests were conducted by admixing the particulated borated gum with the proper amount of water and thereafter adding a pH control agent, e.g. a soluble carbonate or hydroxide, when used, followed by a suspending agent, e.g. an acrylamide polymer to the aqueous dispersion of gum.

Example 1 500 pounds of particulated hydrophobically-treated guar gum (prepared according to US. Pat. 2,868,664) were admixed with pounds of linear polyacrylamide, about 30% hydrolyzed (purchased under the trademark Separan NP30) and enough water to make 1,000 gallons at the ambient temperature of about F. One portion of the slurry composition so made was tested at 250 F. for working time (time elapsed between mixing and state of gel taken as 100 poises) recorded in minutes according to the procedure of Schedule 19 of Section 10 of API RP 10B. A second portion was tested for plug life as above described.

A series of tests (Nos. 2-6, Table I) were conducted at a temperature of 250 F. and an increasing amount of soda ash (commercial grade Na CO was admixed with the borated guar gum prior to admixture of the poly acrylamide.

A second series of tests (Nos. 7 and 8 and Table I) were conducted at a temperature of 250 F. employing Ca(OH) instead of soda ash.

Test No. 9, Table I, was conducted as in the second series except that the temperature of the test was 265 F. and the plug life was determined according to Schedule 20 of Section 10 of RFPI RP 10B.

In the next series of tests (Nos. 1019), the tests were conducted according to the procedure followed in Test No. 9 except that the temperature of the test was 300 F. and either soda ash or Ca(OH) was admixed with the borated guar gum before admixing the polyacrylamide therewith.

In the final series of tests (Nos. 20 and 21) tests were conducted according to the procedure in the previous series except the temperature employed was 325 F. and the Schedule of Section 10 of API RP 10B followed was Schedule 21.

The results of these tests are shown in Table I.

TABLE I [500 pounds of borated guar gum and 50 pounds of acrylamide polymer per 1,000 gallons of dispersion] Additive in pounds pH value Working time in minutes to Section 10 API per 1,000 gallons when Temperature reach 100 RP 1013 sched- Test number of composition made up of test in F. poises ule followed Plug life None 8.6 19 4.5 days NagCOa 19 4.5 days NaaCOa 9.3 19 6.5 days NazCOa 9.8 19 7.0 days NazCOa 10.1 19 8.0 days N11 00:; 10.15 19 8.0 days Ca(OH), 10.0 19 5.5 days Oa(OH)1 19 8.0 days Ca(0H) 11.7 20 8.5 days NazCO 9.3 21 23.5 hours Na OO 21 28.5 hours. NazCO; 10.1 21 20.0 hours. NazCO 10.4 21 24.0 hours ago 3 10.5 21 20.0 hours NazCO 10.5 21 64.01101115 094011); 21 32hours Ca(OH)g 11.8 21 74 hours CaOH); 11.9 21 78 hours Ca OH); 12.0 21 85 hours 021(011), 12.0 21 ohours Ca(0H) 12.4 21 10 hours at which time the ball became firmly in an immobile state by the gelled composition, and thereafter the periodic inversion further continued until the gell broke and again allowed the ball to fall freely. The sound of the ball striking the cap at the bottom of the nipple when inverted indicated that the gel had liquefied, and this was recorded as the plug life. The reliability of this test was also confirmed by opening the system and observing the state of e dmixtu e.

Example 2 In this example, tests were conducted similarly to those in Example 1 except that 750 pounds of a borated galactomannan gum (as exemplified by borated guar gum) were used and the temperature of each test was increased by 25 Fahrenheit degrees as shown in Table Reference to Tables I and H shows that a high temperature plug can be made at temperatures from 175 F. to 325 F., employing a borated galactomannan gum and a polyacrylamide polymer. It can be seen that the higher the temperature, the faster the composition gels. However, it is shown that the rate of gel can be retarded by the use of such alkaline materials as sodium carbonate and Ca(OI-I) The tables also show that as little as 25 pounds of an acrylamide polymer both suspends the borated galactomannan gum and also imparts a moderate increase in pH value to provide an adequate working time within a temperature range of between about 175 F. and about 200 F. At above about 225, the acrylamide polymer concentration is best increased to at least about 50 pounds per 1,000 gallons of composition. It is preferable that the amount be increased to about 75 pounds, per 1000 gallons of gelable composition, at temperatures approaching 300 F. and above.

The degeneration or dissolution of the plug after emplacement occurs over a predetermined period of time. The higher the ambient temperature of the emplaced plug, the more rapid the degeneration of the plug. For example, a composition comprising 500 pounds of the borated guar gum and 50 pounds of the polyacrylamide polymer, the following conditions obtain: at 175 F., it remains solid up to about 28 days; at about 225 F. for about 16 days; at about 250 F. for about days. This length of time for dissolution or disintegration (gel-breaking) of the plug is usually longer than is desirable. Therefore, less alkaline material, e.g. Ca(OH) or Na CO is admixed therewith to delay the gelbreaking period.

It is shown in the tables also that, at temperatures above about 250 F., the working time of the aqueous suspension of the borated galactomannan gum containing the acrylamide polymer in the absence of the alkaline material to raise the pH value, is too short for common use. It is shown, however, that the addition of Ca(O-H) or Na CO lengthens the working time. Accordingly, the addi tion of such alkaline materials provide the attainment of both objectives: an increased working time and lengthened plug life, as desired.

It is also shown that plug life, above a temperature of about 275 F., may be increased by increasing the borated galactomannan gum employed, say on the order of about 750 pounds thereof per 1,000 gallons of aqueous composition being prepared.

Example 3 In this example tests were conducted to show the effect of increasing the concentration of borated galactomannan gum in water and of admixing therewith varying amounts of Ca(OH) The procedure followed was to slurry the borated gum, herein borated guar gum, in the amount given in Table III below, with the amount of water necessary to give the desired concentration, admix therewith the Ca(OH) when employed, and thereafter admix pounds of a suspending agent comprising polyacrylamide (about 30% hydrolyzed) and having an average molecular weight of between 2 and 3 million, known commercially as under the trademark Separan AP 30. The slurry so made was then placed in tubes and immersed in an oil bath, which had been preheated to 225 F. The composition was observed to gel and then further observed so as to determine the time which elapsed before the gel broke.

It was considered broken, when the viscosity dropped to under 10 poises.

The results are shown in Table III.

TABLE III Pounds of Pounds of borated guar Ca(OH)zadded gum per 1,000 per 1,000

gallons of gallons of Plug life Test Number composition composition in day Q 50 None 3 100 None 5 200 None 1 300 None 14 I Reference to Table III shows that the plug life is lengthened as the amount of borated gum is increased. It also shows that the plug life is increased by raising the pH value of the slurry by admixing therewith an hydroxyl ion source, e.g., soluble hydroxide.

Example 4 A further series of tests was conducted to illustrate some alkaline materials that may be used in the practice of the invention to delay the gelation rate and retard the rate of degradation or degeneration of the plug back to a fluid. The procedure followed was to admix the metal hydroxide with water in the proportion of pounds of hydroxide per 1,000 gallons of composition; admixing borated guar gum with the aqueous hydroxide solution in a proportion of 500 pounds of the gum per 1,000 gallons of composition; and then admixing an acrylamide polymer (same as employed in Example 3) in an amount of 50 pounds per 1,000 gallons of composition. The mixture was then transferred to %-inch diameter, 6-inch long steel nip ples each containing a %-inch ball. Thereafter the nipples, as in the plug life tests above, were capped on both ends and placed in an oil bath, previously heated to 275 F. The nipples were thereafter periodically inverted as above described when the composition was gelled, the ball became immobile. When the gel later broke, (the break point being considered occurring at a viscosity less than 50 poises) the ball fell with a clearly audible impact to the bottom of the nipple when inverted.

Table IV sets out the results.

Reference to Table IV shows that various metal hydroxides extend the life of the plug composition of the invention when admixed with the borated gum and the thickening agent is thereafter admixed therewith.

Example 5 This series of test was run to show the use of a cellulose derivative viz, hydroxy ethyl cellulose, as a thickening agent in the composition of the invention. The procedure followed consisted essentially of admixing the amount of hydroxyl ion source, viz Na CO or Ca(OH) 11 with water and therefor admixing the amount of hydroxy ethyl cellulose (abbreviated HEC) set out in Table V below. The pH of the freshly prepared composition, the time in minutes for the composition to reach 100-poise viscosity (taken as the gel point) and the plug life are set aqueous CaCl employing a pressure of 1000 psi. and the temperature designated in Table VI. The amount of borated guar gum employed in each test was that suflicient to provide 500 pounds per 1000 gallons of composition. The amount of polyacrylamide suspending agent 5 out m Table V. and 'hydroxyl 1011 source are shown in Table VI. The

TABLE V Pounds of borated guar Pounds of Working time Temperagum per 1,000 EEC/1,000 Pounds of retarder in minutes ture e gallons of gallons of per 1,000 gallons pH Value b to reach Test number in F. composition composition of composition when made 100 poises Plug life 200 300 50 None 250 300 60 11 NazCOs 250 300 50 16 NazOOs 250 300 50 20 NazCO 250 600 50 NazCOs 275 300 50 15 NazCOa 10 275 500 50 22. 5 NazCOr 10. 5 275 500 50 27. 5 NazCOa 10. 5 275 500 50 32. 5 NazOOs 10. 5 100 45 hours. 275 500 50 50 Ca(OH)a 11. 5 170 5 days. 300 500 None 30 Ca OH): 87 18 hours. 300 500 None 40 Ca OH): 105 hours. 300 500 50 45 Ca OH); 11. 5 107 26 hours.

I Squeeze Schedule No. 19 API RP 10B applicable at 250 F.

Squeeze Schedule No. 20 API RP 10B applicable at 275 F. Squeeze Schedule No. 21 API RP 10B applicable at 300 F. b pH Values were determined bb Hydrion pH paper.

Reference to Table V shows that a cellulose derivafluid loss 1n minutes and the total volume of liquid comtrve, e.g. hydroxy ethyl cellulose, 1s satisfactory as the positlon through the core are also set out 1n Table VI.

TABLE VI Ingredients per 1,000 gallons of aqueous composition Total volume Perme- Fluid loss in m1. afterin ml. through Poly. 1 e fluid ability Tempercell, corrected Test acrylloss control Added hydroxyl to air ature, 1 4 9 16 25 180 for 23.5 cm. Number amide polbmer ion source in md. F. mm. min. min. min. min. min. area 25 578 175 15. 5 28. 5 38. 0 Out of fluid 2,5 667 175 10. 0 19. 5 27. 0 31 35 36 158. 4 25 675 200 10 18 22 24 24. 5 25 110 25 680 200 5 10 12. 5 13 13. 5 15 66. 0 50 590 225 8 18 19. O 19 19 19 83. 6 50 642 225 5 7 7 7 7. 5 8. 0 35. 2 50 635 250 10 15 20 22 24 24 105. 6 50 0 635 250 5 9. 5 12. 5 14 14. 16 70. 4 50 None 75 lbs. of Ca(OH): 632 275 3 4 5 6. l 6. 2 9. 8 43. 1

I J polymer is 60% vinylpyrrolidone and 40% acrylamide copolymerlzed with 0.7% N ,N-methylenebisacrylamide as a crosslinking agent.

suspending agent in the composition of the invention and further that the hydroxyl ion sources, as represented by Na CO and Ca(Ol-I) perform substantially as efliciently in the presence of hydroxy ethyl cellulose as in presence of polyacrylamide.

Example '6 'Reference to Table VI shows that fluid loss from the ungelled composition is greatly lessened by the presence of the specific vinylpyrrolidone-acrylamide crosslinired with methylenebisacrylamide in the amounts shown.

Example 7 It is sometimes desirable that the gelled composition be extruded as, for example, in treating formations comprising vugs and impacked fractures. In such instances, it is desirable that the plug resist up to about pounds or more pressure but that it extrude into the vugs and fractures at relatively high pressures, thereby to serve as an excellent diverting agent for fracturing fluids but which subsequently disintegrates and no longer acts as a plug.

To show that the gelled composition can be extruded into larger openings, e.g. to 4 inch in cross section to simulate vugs and large fractures, tests were performed as follows:

TABLE VII Pounds of cellophane flake per 1,000 Hydraulic Extrusion through pipe having diameter ofgallons of Temp. pressure Test Number composition F.) (p,s.i.) inch M inch inch None 225 20 Rapid. 1 inch in 10 see No movement. None 225 50 D0. N one 225 100 1 inch in 30 sec.

25 225 20 Rapid 1 inch in 10 sec N o movement. 25 225 100 0. 25 225 200 Held for 3 min. and then extruded rapidly. 100 225 20 Rapid 1 inch in 15 sec No movement. 100 225 200 Do. 100 225 1, 700 Held for 2 min. and then extruded rapidly.-

A 12-inch long, 2-inch diameter pipe nipple was equipped with caps. The lower cap contained threaded A, ;3 and r-incl1 diameter openings. The openings which were not being tested were plugged.

14 (b) polyacrylamide suspending agent about 20 to 60 parts; and (c) an effective amount of sodium bicarbonate. 8. A granulated composition of matter consisting es- The gelable composition of the invention consisted essentially of as parts by weight:

sentially of borated guar gum, polyacrylamide (average weight between about 1,000,000 and 3,000,000) and water to make proportions of 500 pounds of the gum and 50 pounds of the polyacrylamide per 1,000 gallons of water.

The composition was poured into the 12-inch by 2-inch pipe and subjected to an advanced temperature for a period of 20 hours and at the pressure shown in the Table VII. Cellophane flake was added in the tests, as shown in the table, as a fluid loss additament.

Reference to Table VII shows that the gelled composition of the invention can be readily extruded into the larger opening and passageways as in an earthen formation being treated, e.g. fractured, where entrance of excessive amounts of the treating fluid into the larger openings is undesired, but will not so readily enter the smaller openings and passageways where entrance of the treating fluid is desired.

It can be seen that the composition of the invention otters the advantages of providing a temporary plug particularly adaptable for use in porous earthen formations, which is fluid when made, can be readily emplaced as needed, then gels to form a plug of temporary nature which is excellent for diverting subsequently injected fluids, and which at high pressures can be forced into relatively larger opening farther removed from the entrance, and thereafter disintegrates to a fluid which can be easily removed and does no formation damage.

What is claimed is:

1. A granulated composition which when dispersed in an aqueous carrier liquid forms a viscous slurry which sets up after a period of time to form a stiff gel which subsequently breaks to form a fiowable material, which consists essentially of, as parts by weight:

(a) from about 50 to about 1500 parts of a particulate hydrophobically treated galactomannan gum so that when dispersed in an aqueous solution having a neutral to alkaline pH the gum does not readily hydrate in its normal length of time;

(b) from about 3 to about 100 parts of a readily water-soluble organic polymeric suspending agent, the suspending action of which is not affected by the hydrophobing agent; and

(c) .03 to about 600 parts of a pH control agent in an amount which is effective to provide an initial pH in an aqueous solution in which the granulated composition is dispersed of at least about 7.5.

2. The composition as defined in claim 1 consisting essentially of:

(a) from about 300 to about 750 parts of said galactomannan gum;

(b) from about 20 to about 60 parts of said suspending agent; and

(c) a butfering agent as the pH control agent.

3. The composition as defined in claim 1 wherein said pH control agent is a hydroxyl ion producing material.

4. The composition of matter as defined in claim 1 wherein said suspending agent consists of a synthetic water-soluble polymer.

5. The composition as defined in claim 1 wherein said (a) galactomanan gum consists of guar gum; and

(b) said suspending agent consists of an acrylamide polymer.

6. The composition as defined in claim 1 wherein said pH control agent is a buffering agent consisting of sodium bicarbonate, NaH PO -Na HPO boric acid-sodium hydroxide. acetic acid-sodium hydroxide, boric acid-borax or sodium carbonate-sodium bicarbonate.

7. The com osition as defined in claim 1 wherein said composition consists essentially of:

(a) a borate treated guar gum from about 300 to 750 parts;

(a) from about 300 to about 750 parts of a particulate galactomannan gum treated with a boron containing compound to render the gum less hydrophillic than normal when dispersed in an aqueous solution having a pH value of at least about 7.5 greater;

(b) a suspending agent consisting of at least one of a water-soluble homopolymer or copolymer of acrylamide or methacrylamide from about 20 to about 60 parts; and

(c) as a pH control agent a material which buffers an aqueous solution to provide a pH value of at least 7.5 or greater.

9. A slurry composition which consists essentially of:

(a) from about 150 to about 1500' pounds of a particulate galactomannan gum which has been treated with an effective amount of a hydrophobing agent so that the gum is less hydrophiliic than normal when dispersed in an aqueous solution having about a neutral to alkaline pH value and has a normal hydrophillic characteristic in aqueous solution having an acidic pH value;

(b) from about 3 to about pounds of a watersoluble organic polymeric suspending agent, said water-solubility of said suspending agent not being affected by said hydrophobing agent and said agent producing about a neutral to alkaline pH value when dispersed in an aqueous solution; and

(c) a sufiicient amount of an aqueous solution to make 1000 gallons of said slurry, said solution being buffered to have an initial pH of at least about 7.5.

10. The slurry composition as defined in claim 9 wherein the treated galactomannan gum is guar, tara or locust bean treated with an effective amount of a material which releases borate ions when dispersed in water.

11. The slurry composition as defined in claim 10 wherein the water-soluble organic polymeric suspending agent is at least one of a water-soluble homopolymer or compolymer of acrylamide or methacrylamide.

12. The slurry composition as defined in claim 11 wherein said treated galactomannan gum is provided in an amount ranging from about 300 to about 750 pounds.

13. The slurry composition as defined in claim 12 wherein said suspending agent is provided in an amount ranging from about 20 to about 60 pounds.

14. The slurry composition as defined in claim 11 wherein said solution is buffered by incorporating in an aqueous solution an effective amount of a buffering agent consisting of at least one of NaI-I PO -Na HPO boric acid-borax, sodium carbonate-sodium bicarbonate, sodium bicarbonate, acetic acid-sodium hydroxide, or boric acidsodium hydroxide.

15. A slurry composition which consists essentially of:

(a) from about 300 to about 750 pounds of a galactomannan gum which is treated with an elfective amount of a material which releases borate ion when dispersed in an acqueous solution to render the gum less hydrophillic than normal when dispersed in an aqueous solution having about a neutral to alkaline pH value and a normal hydrophillic characteristic when dispersed in an aqueous solution having an acidic pH value;

(b) a water-soluble organic polymeric suspending agent of at least one of a water-soluble homopolymer or compolymer of acrylamide or methacrylamide from about 20 to about 60 pounds;

(c) an effective amount of buffering agent, said buffering agent is at least one of NaH PO' -Na HPO boric acid-borax, boric acid-sodium hydroxide, sodium carbonate-sodium bicarbonate, sodium bicarbonate or acetic acid-sodium hydroxide; and

make about 1000 gallons of said slurry composition.

References Cited UNITED STATES PATENTS Nimerick 106-209 Walker 252-85 Pence 166-295 Parks 175-65 Lindblom et a1. 17s-72 Goldstein 106-208 Mogg 106-209 Horner et a1. 175-72 16 Braunlich et al. 175-72 Wyant et al 252-855 X Wyant 252-85 Walker 252-311 Morgan 252-85 Kern 252-855 WILLIAM H. SHORT, Primary Examiner E. WOODBERRY, Assistant Examiner US. Cl. X.R.

UNITED STATES PA'l'rjNl' Ur'ritr. CERTIFICATE OF (ZQRREC'HQN Patent No. 3,743,613 Dated July 3, 1973 Inventor(s) Albert W. Coulter, Jr. Daniel L. Gibson & Kenneth H.

Nimerick It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 2, line 61, delete "paloverde" and insert paloverale-. 1

Column 3, line l9, delete "atfer" and insert --after-.

Column 3, line 66, delete "include" and insert includes--.

Column 5, line 36, delete "volunm" and' insert -column--.

Column 8, line 25, delete "7 and 8'and Table I" and insert 7 and 8 Table I- Column '8, line' 31, delete "RFPI" and insert --RPI-.

Column 8, line 75, after "'IIZ' insert The resulted working time and plug life tests are also shown in Table II-.

Column 10, line 26, after "e.g. insert --.a-.

Column 11, Table V, footnote b, delete "bb" and insert by-.

Column ll, Table VI, 3rd column, delete "polbmer" and insert -polymer-. I

Column 12, Table V, 6th column, (Test No. 50) insert --7.58----;

(Test No. 51), insert Column 14, line 10, after "7.5 insert or.

Signed and sealed this 26th day of March l97L (SEAL) Attest:

EDWARD MJ LETCHERJR. C. MARSHALL DANN Attesting Officer Commissionerof Patents UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTICN Patent No. 3,743,613 Dated July 3, 1973 Inventor(s) Albert W. Coulter, Jr. Daniel L. Gibson & Kenneth H.

Nimerick It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 2, line 61, delete "paloverde" and insert -paloverale--.

Column 3, line 19, delete "atfer'i and insert --after--.

Column 3, line 66, delete "include" and i nsert includes-.

Column 5, line 36, delete "volumn" and insert column--.

Column 8, line 25, delete "7 and 8 and Table I" and insert -7 and 8 Table I-.

Column-8, line 31, delete "RFPI" and insert --RPI-.

Column 8, line 75, after "III' insert -The resulted working time and plug life tests are also shown in Table II-.-

Column 10, line 26, after "e.g.," insert -a-.

Column 11, Table V, footnote b, delete "bb" and insert by--.

Column 11, Table VI, 3rd column, delete "polbmer" and insert polymer--.

Column 12, Table V, 6th column, (Test No. 50) insert 7.5-8--;

(Test No. 51) insert Column l4, line 10, after "7.5" insert -or--.

Signsd and sealed this 26th day of March 197L (SEAL) Attest:

EDWARD M.FLETCHER,JR. C. MARSHALL DANN Attesting Officer Commissioner of Patents 

